Photographic elements containing amino-substituted hydroxy-pyridones

ABSTRACT

Pyridone dyestuffs of the formula ##STR1## are provided wherein R 1  is hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or an optionally substituted amino group, 
     R 2 , R 3 , R 4  each independently represent hydrogen, halogen, alkoxy, or optionally substituted alkyl or cycloalkyl, 
     R 5  and R 6  each independently represent hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or R 5  and R 6 , R 3  and R 5  and R 4  and R 6  form heterocyclic rings, 
     Y is hydrogen or hydroxy, --CN, --COOR 7 , --CONR 7  R 8  or --COR 7  or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, and 
     Z represents --CN, --COOR 9 , --CONR 9  R 10 , --SO 3  H, --SO 3  ⊖ or --COR 9 , where R 7 , R 8 , R 9  and R 10  each independently represent hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical. 
     The dyestuffs can be used e.g. as cyan image dyestuffs in photographic material, as diffusible dyes which may become mordanted in a receptor layer or as filter, antihalation or acutance dyes in photographic material.

This is a division, of application Ser. No. 879,425 filed Feb. 21, 1978,now U.S. Pat. No. 4,182,886.

This invention relates to novel dyestuffs, to their production and totheir use in photographic materials.

According to the present invention there are provided dyestuffs to theformula ##STR2## wherein R₁ is hydrogen or an optionally substitutedalkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or anoptionally substituted amino group,

R₂, R₃, R₄ each independently represent hydrogen, halogen, alkoxy, oroptionally substituted alkyl or cycloalkyl and R₅ and R₆ eachindependently represent hydrogen, or an optionally substituted alkyl,aralkyl, cycloalkyl, aryl or heterocyclic radical or R₅ and R₆ togetherwith the nitrogen atom to which they are attached form a 5- or6-membered nitrogen containing heterocyclic ring, or R₃ and R₅ togetherform with the nitrogen atom a 5- or 6-membered nitrogen containingheterocyclic ring, or R₄ and R₆ together form with the nitrogen atom a5- or 6-membered nitrogen containing heterocyclic ring, or R₃ and R₅together with the nitrogen atom and R₅ and R₆ together with the nitrogenatom form two nitrogen containing heterocyclic rings,

Y is hydrogen or hydroxy, --CN, --COOR₇, --CONR₇ R₈ or --COR₇ or anoptionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclicradical, and

Z is --CN, --COOR₉, --CONR₉ R₁₀, --SO₃ H, --SO₃ .sup.⊖ or --COR₉ group,where R₇, R₈, R₉ and R₁₀ each independently represent hydrogen or anoptionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclicradical.

Throughout the specification the terms lower alkyl and lower alkoxy areused to denote alkyl or alkoxy radicals respectively containing from 1to 6 carbon atoms.

The optionally substituted alkyl radicals represented by Y, R₁ to R₁₀are preferably lower alkyl groups or substituted lower alkyl radicals,and as specific examples of such radicals there may be mentioned methyl,ethyl, n-propyl, n-butyl, n-octyl, n-decyl and n-dodecyl, hydroxy loweralkyl such as β-hydroxymethyl, lower alkoxy alkyl with 1 to 6 carbonatoms in the alkoxy and alkyl radical such as β-(methoxy orethoxy)-ethyl and γ-methoxypropyl, cyano lower alkyl such ascyanomethyl, carbamoylmethyl, carbethoxymethyl, and acetylmethyl.

As examples of aralkyl radicals represented by Y, R₁ and R₃ to R₁₀ theremay be mentioned benzyl and β-phenyl ethyl.

As an example of a cycloalkyl radical represented by Y and R₁ to R₁₀there may be mentioned cyclohexyl. The optionally substituted arylradicals represented by Y, R₁ and R₅ to R₁₀ are preferably phenyl oroptionally substituted phenyl radicals, and as specific examples of suchradicals there may be mentioned phenyl, tolyl, chlorophenyl,methoxyphenyl and ethoxyphenyl. The optionally substituted heterocyclicradicals represented by Y, R₁ and R₅ to R₁₀ are preferably 5- and6-membered heterocyclic rings and as specific examples of such radicalsthere may be mentioned 2-pyridyl, 2-thiazolyl, 1-piperidinyl and1-morpholinyl, each of which may be substituted.

As examples of 5- and 6-membered heterocyclic rings formed by joining R₅and R₆ and the nitrogen atom, or R₃ and R₅ and the nitrogen atom, or R₄and R₆ and the nitrogen atom, there may be mentioned piperidine,morpholine, piperazine and pyrrolidine.

Z is preferably --CN, --COOR₁₁ or --CONR₁₁ R₁₂ wherein R₁₁ and R₁₂ arehydrogen or alkyl of 1 to 3 carbon atoms.

Of special interest are further dyestuffs of formula (1), wherein R₁ ishydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1 to 6 carbonatoms, alkoxyalkyl of 1 to 6 carbon atoms each in the alkyl and thealkoxy radical, phenyl, benzyl, β-phenylethyl or cyclohexyl, R₂ ishydrogen, chloro, alkyl, hydroxyalkyl or alkoxy each of 1 to 6 carbonatoms, R₃ is hydrogen, alkyl or alkoxy of 1 to 6 carbon atoms, R₄ ishydrogen or alkyl of 1 to 6 carbon atoms, R₅ and R₆ are hydrogen, alkylor hydroxyalkyl of 1 to 6 carbon atoms, alkoxyalkyl of 1 to 6 carbonatoms each in the alkyl and the alkoxy radical, carboxyalkyl with 1 to 3carbon atoms in the alkyl radical, β-methylsulphonamidoethyl orsulpho-n-butyl, Y is hydrogen, cyano, carbmethoxy, carbethoxy,carbonamido or alkyl of 1 to 6 carbon atoms and Z is cyano, carbmethoxy,carbethoxy or carbonamido.

Preferred dyestuffs of the present invention are those of the formula##STR3## wherein R₁ is alkyl of 1 to 6 carbon atoms, R₂ is hydrogen oralkyl of 1 to 3 carbon atoms, R₅ and R₆ are alkyl of 1 to 4 carbonatoms, hydroxyalkyl of 2 to 4 carbon atoms or R₅ and R₆ together withthe nitrogen atom to which they are attached are a piperidine,morpholine, piperazine or pyrrolidine ring and especially such offormula (2), wherein R₁ is alkyl of 1 to 6 carbon atoms, R₂ is hydrogenor methyl and R₅ and R₆ are ethyl or hydroxyalkyl of 2 to 4 carbonatoms.

The following single species are especially preferred: Dyestuffs of theformula ##STR4##

According to a further feature of the invention there is provided aprocess for the manufacture of the dyestuffs of formula (1) whichcomprises condensing a hydroxypyridone of the formula ##STR5## whereinY, Z, and R₁ have the meanings hereinbefore stated and X is hydrogen orhalogen or a coupling-off group as hereinafter defined with a colourdeveloper of formula ##STR6## where R₂ to R₆ have the meaningshereinbefore stated, in the presence of an oxidising agent and base.

By `coupling-off group` is meant a group present in the couplingposition X which is released when the colour coupler couples withoxidised colour developing agent. A particular example of a coupling-offgroup is a mercapto radical.

An example of a coupling-off group is the group Q--T where Q is anoxygen or sulphur linking atom and T is an optionally substituted alkyl,aryl or heterocyclic group or where Q is a direct link and T is a group##STR7## where W represents the atoms necessary to complete a 5- or6-membered heterocyclic ring.

As examples of oxidising agents may be mentioned ammonium persulphate,potassium ferricyanide, and silver halide.

As examples of suitable bases may be cited sodium hydroxide, potassiumcarbonate, and pyridine.

The hydroxypyridones of formula (6) used in the process of the inventioncan themselves be obtained by a number of methods such as are describedfor example in "Heterocyclic Compounds--Pyridine and itsderivatives--Part 3" which was edited by Klinsberg and published byInterscience Publishers in 1962. See also B.P. No. 1,256,095.

The colour developers used in the process of the present invention areof the usual type employed in chromogenic photographic development suchas are described for example in "The theory of the photographic process"(chapter 13) edited by Mees and James and published by MacMillan in1966.

As specific examples of the hydroxypyridones there may be mentioned2,6-dihydroxy-3-cyano-4-methylpyridine, 1-(methyl orethyl)-3-cyano-4-methyl-6-hydroxy-pyrid-2-one, 1-(β-hydroxyethyl orγ-methoxy-propyl)-3-cyano-4-(methyl, phenyl orethyl)-6-hydroxypyrid-2-one, 1-(phenyl, or -anisyl)-3-cyano-4-(methyl orphenyl)-6-hydroxy-pyrid-2-one, 1-phenyl-3-(carbonamido orcarboethoxy)-4-(methyl or phenyl)-6-hydroxypyrid-2-one,2,6-dihydroxy-3-(carboethoxy or carbodiethylamido)-4-methylpyridine,2,6-dihydroxy-3-(carbonamido or carboethoxy)pyridine,2,6-dihydroxy-3-carbonamido-4-phenylpyridine,2,6-dihydroxy-3-cyano-4-carbonamidopyridine,2,6-dihydroxy-3-cyano-4-(carbomethoxy or carboethoxy)pyridine, ethyl2,6-dihydroxy-3-cyanopyrid-4-ylacetate,2,6-dihydroxy-3-cyanopyrid-4-ylacetamide,2,6-dihydroxy-3,4-di(carboethoxy)-pyridine,2,6-dihydroxy-3-carbonamido-4-carboethoxy-pyridine, ethyl2,6-dihydroxy-isonicotinate, 2,6-dihydroxy isonicotinamide,2,6-dihydroxy isonicotinic acid diethylamide, and2,6-dihydroxy-3-cyano-4-ethoxy-carbonyl-1-methyl-pyridine.

As specific examples of colour developers there may be mentioned:

4-Amino-2-acetamido-N,N-diethylaniline

4-Amino-2-methyl-N,N-diethylaniline

4-Amino-2-methyl-N,N-dimethylaniline

4-Amino-2,5-dimethyl-N,N-diethylaniline

N-(4-Aminophenyl)morpholine

2,4-Diamino-N,N-diethylaniline

N-(4-Aminophenyl)piperazine

N-(4-Amino-3-methylphenyl)morpholine

4-Amino-N-ethyl-N-carbamoylmethylaniline

4-Amino-2-methoxy-N,N-diethylaniline

4-Amino-3-chloro-N,N,-diethylaniline

4-Amino-3-methyl-N-ethyl-N-carbamoylmethylaniline

N-(4-Aminophenyl)piperidine

4-Amino-N-ethyl-N-(β-methoxyethyl)aniline

4-Amino-N-ethyl-N-(β-acetamidoethyl)aniline

4-Amino-N-ethyl-N-(N-methyl-β-methylsulphonamido-ethyl)aniline

4-Amino-N-ethyl-N-(β-ethoxyethyl)aniline

N-(4-Amino-3-methylphenyl)piperidine

4-Amino-2-methoxy-5-methyl-N,N-diethylaniline

4-Amino-N,N-dimethylaniline

4-Amino-N-ethyl-N-tetrahydrofurfurylaniline

4-Amino-N-methyl-N-ethylaniline

4-Amino-N-methyl-N-(η-butyl)aniline

4-Amino-N-methyl-N-(η-propyl)aniline

4-Amino-3-methyl-N-ethyl-N-(N-methyl-β-methyl-sulphonamidoethyl) aniline

4-Amino-N,N-diethylaniline

4-Amino-3-methylsulphonamidoethyl-N,N-diethyl-aniline

4-Amino-N-ethyl-N-(β-methylsulphonamidoethyl)aniline

4-Amino-3-hydroxymethyl-N,N-diethylaniline

4-Amino-N-ethyl-N-(η-propyl)aniline

4-Amino-3-(β-acetamidoethyl)-N,N-diethylaniline

4-Amino-3-(β-hydroxyethyl)-N,N-diethylaniline

4-Amino-3-(β-aminoethyl)-N,N-diethylaniline

4-Amino-N-ethyl-N-(β-hydroxyethyl)aniline

4-Amino-N,N-di(η-propyl)aniline

4-Amino-N-ethyl-N-(β-aminoethyl)aniline

4-Amino-3-methyl-N-methyl-N-(β-methyl sulphonamidoethyl)aniline

4-Amino-3-ethyl-N,N-diethylaniline

4-Amino-3-(N-methyl-β-methylsulphonamidoethyl)-N,N-diethylaniline

1-(4-Aminophenyl)pyrrolidine

4-Amino-3-methyl-N-ethyl-N-tetrahydrofurfuryl-aniline

4-Amino-3-(β-methylsulphonamidoethyl)-N,N-diethylaniline

4-Amino-3-acetamido-N,N-diethylaniline

4-Amino-3-methyl-N-ethyl-N-(β-methylsulphonamidoethyl)aniline

4-Amino-3-methyl-N,N-diethylaniline

6-Amino-1-(β-methylsulphonamidoethyl),1,2,3,4-tetra-hydroquinoline

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline

6-Amino-1-ethyl-,2,3,4-tetrahydroquinoline

4-Amino-3-ethoxy-N-ethyl-N-(N-methyl-β-methylsulphonamidoethyl) aniline

5-Amino-1-(β-methylsulphonamidoethyl)indoline

4-Amino-3,5-dimethyl-N,N-diethylaniline

4-Amino-3-ethoxy-N-ethyl-N-(β-methylsulphonamidoethyl)aniline

4-Amino-3-methoxy-N,N-diethylaniline

4-Amino-3-ethoxy-N,N-diethylaniline

9-Aminojulolidine

4-Amino-3-dimethylamino-N,N-diethylaniline

4-Amino-3-methylsulphonamido-N,N-diethylaniline

3,4-Diamino-N,N-diethylaniline

4-Amino-3-ethylamino-N,N-diethylaniline

4-Amino-3-hydroxy-N,N-diethylaniline

The preparation of the compounds of the invention can be convenientlycarried out by stirring the reactants together in water or an organicsolvent such as pyridine. The resulting dyestuff can then be isolated byconventional methods.

The dyestuffs of the present invention may be used in photographicmaterials in a large number of different ways. For example they may bepresent as image dyestuffs in silver halide colour photographicmaterial. In this case the dyestuffs are formed in situ in thephotographic material as a result of the colour development process andthe photographic material is in this case an exposed and processedmaterial bearing a dye image.

The dyestuffs of the present invention find most use as filter oranti-halation dyes in which case the pre-formed dyes are present in theunexposed and unprocessed photographic material.

Therefore according to this aspect of the present invention there isprovided light-sensitive photographic material which comprises in atleast one layer thereof a dyestuff of the general formula (1).Optionally the dye in this aspect of the invention is present as an oildispersion in a binder layer.

The dyestuff of formula (1) may be present in a resin binder as ananti-halation backing layer on the reverse side of the film base to thephoto-sensitive layer.

Dyestuffs of formula (1) of particular use in antihalation backinglayers have the formula (2).

A particularly useful dyestuff of formula (1) as an antihalation backingdye has the formula (3). Examples of suitable resin binders are nitratedstyrene-maleic acid copolymer, styrene-methacrylic acid copolymer, vinylacetate-crotonic acid copolymer and sulphonated polystyrene.

The dyestuff of formula (1) and especially of formula (2) may be presentin an anti-halation underlayer of the photographic material that is tosay between the film base and the lowest light-sensitive layer. In thiscase either the dye is substantive to the layer, either intrinsically orby virtue of being dissolved in an oil, but is bleached in a processingbath and the bleached residue washed out of the photographic material orthe dyestuff is mordanted in the layer and the dye-mordant bond isbroken in a processing solution so that the dye can be washed out of thephotographic material.

Readily bleachable dyestuffs of formula (1) are those wherein Z is anelectron withdrawing group such as --CN, --COOR₉, --CONR₉ R₁₀ or --COR₉where R₉ and R₁₀ have meanings given to them before and R₁ is anoptionally substituted lower alkyl group.

Especially preferred bleachable dyestuffs correspond to formula (1),wherein Y is CH₃, Z is --CN, --COOR₁₁ or --CONR₁₁ R₁₂, R₁ is alkyl of 1to 6 carbon atoms, R₂ is hydrogen or alkyl of 1 to 3 carbon atoms, R₃and R₄ are hydrogen and R₅ and R₆ are alkyl of 1 to 4 carbon atoms,hydroxyalkyl of 2 to 4 carbon atoms or R₅ and R₆ together with thenitrogen atom to which they are attached are a piperidine, morpholine,piperazine or pyrrolidine ring.

Dyestuffs of formula (1) which can be mordanted and which are diffusibleafter the mordant bond is broken are those which contain an acidicsubstituent group.

A particularly suitable readily bleachable dyestuff of formula (1) hasthe formula (4).

This dye absorbs light in the region of 400-700 nm in gelatine and thusis suitable for use in an anti-halation underlayer.

Examples of binding agents suitable when the dyes of the presentinvention are used as anti-halation underlayers are gelatiin and gelatinderivatives.

The diffusible dyestuffs of formula (1) may also be used as acutancedyes in photographic material in which case they diffuse throughout thelayers in the photographic material and absorb any stray light duringexposure and thus help to increase the sharpness of the final image.

The dyestuffs of general formula (1) and especially of formula (2) maybe also used as filter dyes in colloid filter layers between lightsensitive layers. A dye particularly suitable for use as an oildispersion has the formula (5). When dissolved in ditertpentylphenol andthe mixture dispersed in gelatin, the combination absorbs light withDmax 530 nm.

EXAMPLE 1 Preparation of the dye of the formula ##STR8##

5.15 g of 1-butyl-3-cyano-6-hydroxy-4-methylpyrid-2-one in 430 mlpyridine were treated with a solution of 14.6 g of4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline in water. 22.82 g ofammonium persulphate, in water was added, the mixture stirred and aprecipitate was formed which was collected by filtration and washed withwater. A slurry of the product in hot ethanol was stirred 5 minutes andthe product filtered off. This procedure was repeated until no startingmaterial showed in a chromatogramme.

The visible spectrum in methanol λ max at 665 nm with a side absorptionat 414 nm.

EXAMPLE 2 Preparation of the dye of the formula ##STR9##

1.29 g of 1-hexyl-3-cyano-6-hydroxy-4-methyl pyrid-2-one and 2 g ofsodium hydroxide were dissolved in 200 ml of water, 2.42 g of4-amino-3-methyl-N-ethyl-N-(p-hydroxyethyl)aniline was added followed byan aqueous solution of 4.48 g of ammonium persulphate. The mixture wasstirred 10 minutes. The blue gum which formed was treated with hotethanol and the mixture poured into water. The precipitate was filteredoff, and treated with hot ethanol until no starting material showed in athin layer chromatogramme.

The visible spectrum in methanol showed λ max at 664 nm with a sideabsorption at 400 nm.

EXAMPLE 3 Preparation of the dye of the formula ##STR10##

1.03 g of 1-butyl-3-cyano-6-hydroxy-4-methylpyrid-2-one in 15 ml of 1 Maqueous sodium hydroxide solution was treated with 10 ml of 1 M4-amino-N-ethyl-N-(β-hydroxyethyl)-aniline and 20 ml of 1 M aqueoussolution of ammonium persulphate. The mixture was stirred 10 minutesfiltered and the precipitate washed with water. The product wasrecrystallised from ethanol.

λ max at 585 and 635 nm; sideband at 410 nm.

EXAMPLE 4 Preparation of the dye of the formula ##STR11##

The same procedure was used as in Example 1 but1-butyl-3-cyano-6-hydroxy-4-methyl-pyrid-2-one was replaced by the1-propyl derivative and the developer used was4-amino-N-ethyl-N-(β-hydroxyethyl)aniline.

λ max at 535 nm. Side-band at 405 nm.

EXAMPLE 5 Preparation of the dye of the formula ##STR12##

The same procedure was used as in Example 4 but the colour developerused was 4-amino-3-methyl-N-ethyl-N(p-hydroxyethyl)aniline instead of4-amino-N-ethyl-N-(β-hydroxyethyl)aniline.

λ max at 645 nm; side-band at 405 nm.

EXAMPLE 6 Preparation of the dye of formula ##STR13##

The same procedure was used as in Example 1 but1-butyl-3-cyano-6-hydroxy-4-methyl-pyrid-2-one was replaced by the1-iso-propyl derivative and the developer used was4-amino-N-ethyl-N(δ-hydroxy-butyl)aniline.

λ max at 590 nm; side-band at 414 nm.

EXAMPLE 7 Preparation of the dye of formula ##STR14##

The same procedure was used as in Example 4 but1-ethyl-3-cyano-6-hydroxy-4-methyl-pyrid-2-one was used instead of the1-propyl derivative.

λ max at 589 nm; side-band at 408 nm.

EXAMPLE 8

In this Example the dyes of Examples 1 to 7 were coated in a layer on tophotographic base material and tested for substantivity and forbleachability.

Dyed coated gelatin layers were prepared as follows:

Stock Solutions

6% Gelatin:

Gelatin: 6 g

Distilled water: 94 ml

Swell at room temperature for 30 minutes and then dissolve at 60° C.

Adjust to 40° C.

Dyestuff: 25.10⁻³ molar

Dissolve 0.25 mMol of the dyestuff in 10 ml of water or2-ethoxy-ethanol. Adjust solution to 40° C.

Hardener: 1%

Dissolve 100 mg of the hardener dichlorotriazine in 10 ml water. Adjustsolution to 40° C.

Wetting agent: 4% alkylsulfosuccinate or 8% sodium salt ofalkylnaphthalene sulfonic acid

Coating Solution:

Gelatin stock solution: 3.5 ml

Distilled water: 5.0 ml

Wetting agent: 0.25 ml

Dyestuff: 0.232 ml

Hardener: 1.0 ml

Coat at 40° C. on plates affixed with triacetate base, and allow to setfor 5 minutes on a cold plate (≃10° C.). Dry at room temperature.

Gel coating weight: 91.3 mg/dm²

mMol Dye/100 g gel: 2.76

Dye coating weight: 0.0025 mMol/dm²

Six samples were prepared using dyes of Examples 1 to 6. Dyed coatedresin layers were prepared as follows:

Dye: 0.25 mM in 10 ethoxyethanol

Resin: 5% solution by weight solution of methylmethacrylate-methacrylicacid copolymer in ethanol/toluene

(95:5 by volume).

A mixture of 0.278 ml dye solution, 1.722 ml resin solution and 0.5 mlethanol was coated on a "subbed 2/1000" polyester base (6.5×23 cm).

Five samples were prepared using dyes of Examples 1 to 5.

Oil dispersions were prepared as follows: A concentrated solution of thedye in oil was dispersed in gelatin.

Dye/oil solution: 10 g

10% gelatin: 80 g

10% sodium salt of alkylnaphthalene sulfonic acid: 20 g

A coating solution was made by diluting the dispersion with 10% gelatinsolution and water to a final concentration of 3%. A triazine hardenerwas added at the rate 130 mmole hardener per gram gelatin.

Coatings were made on a triacetate base and incubated 16 hours at 40° C.and 56% RH (relative humidity).

Four samples were prepared from the dye of Example 7.

Substantivity Measurement

A 5 cm² disc was cut and the visible spectrum measured. The disc wassoaked in water (7.5 ml) for 30 minutes. The disc was allowed to dry andthe specimen measured again. ##EQU1## Bleachability Measurement

For simple gelatin and resin coatings:

A strip (2.54×7.62 cm) was immersed 2.5 minutes in developer, 2 minutesin fixer and washed 10 minutes in water before drying.

The developer solution comprised per liter aqueous solution 2 g ofN-methyl-p-aminophenol sulfate, 75 g of anhydrous sodium sulphiate, 8 gof hydroquinone, 37.5 g of anhydrous sodium carbonate and 2 g ofpotassium bromide. The fixer consisted 82 g of ammonium thiosulphate perliter aqueous solution. For oil dispersed gelatin coatings:

A strip (2.54×7.62 cm) was immersed 3.25 minutes in developer, 6.5minutes in bleach, and washed 3.25 minutes in water; all operations at atemperature of 37.8° C. The strip was immersed 6.5 minutes in fixer,washed 3.25 minutes in water and treated with stabiliser for 1.5 minutesbefore drying.

The developer solution comprised per liter aqueous solution 4.75 g of4-amino-3-methyl-N-ethyl-N-hydroxyethylanilino hydrogen sulfate, 4.25 gof anhydrous sodium sulphite, 3.75 g of anhydrous potassium carbonate, 2mg of potassium iodide, 1.3 g of sodium bromide, 2 g of hydroxylaminesulphate and 2.5 g of sodium hexametaphosphate. The bleach consisted of150 g of ammonium bromide, 35 g of sodium nitrate, 1.56 M (1/5 ml) offerric ammonium ethylenediaminetetraacetate, and 10.5 ml of acetic acidper liter solution. The fixer consisted of 162 ml of an aqueous 50%solution of ammonium thiosulphate, 1.25 g ofethylenedinitrilotetraacetic acid disodium salt, 12.4 g of anhydroussodium bisulphite, and 2.4 g of sodium hydroxide per liter water. Thestabiliser comprised 5 ml of an aqueous formaldehyde solution (37%) and0.8 ml of a wetting agent per liter solution. ##EQU2##

The following results were obtained:

    ______________________________________                                                           Light absorp-                                                                            Substan-                                                                             Bleach-                                            Dye      tion in layer                                                                            tivity ability                                  Coating   (formula)                                                                              (nm)       %      %                                        ______________________________________                                        Gelatin   101      450/600     80    98                                       "         103      472        100    100                                      "         104      475/585    100    97                                       "         105      430/592     35    96                                       "         106      400-700    100    100                                      Resin     101      600-680    100    100                                      "         102      645        100    96                                       "         103      580        100    100                                      "         104      580        100    100                                      "         105      405/586    100    93                                       Oil(Reofos 65,                                                                Trademark)                                                                              107      590         89    94                                       Oil(ditert-                                                                   pentylphenol)                                                                           107      666         92    88                                       Oil(n-butyl-                                                                  acetanilide)                                                                            107      586         76    52                                       Oil(diethyl-                                                                  lauramide)                                                                              107      583         84    87                                       ______________________________________                                    

We claim:
 1. Light-sensitive photographic material which comprises in atleast one layer thereof a dyestuff of the general formula ##STR15##wherein R₁ is hydrogen, alkyl of 1 to 6 carbon atoms, hydroxyalkyl of 1to 6 carbon atoms, alkoxyalkyl of 1 to 6 carbon atoms each in the alkyland the alkoxy radical, phenyl, benzyl, β-phenylethyl or cyclohexyl, R₂is hydrogen, chloro, alkyl, hydroxyalkyl or alkoxy each of 1 to 6 carbonatoms, R₃ is hydrogen, alkyl or alkoxy of 1 to 6 carbon atoms, R₄ ishydrogen or alkyl of 1 to 6 carbon atoms, R₅ and R₆ are hydrogen, alkylor hydroxyalkyl of 1 to 6 carbon atoms, alkoxyalkyl of 1 to 6 carbonatoms each in the alkyl and the alkoxy radical, carboxyalkyl with 1 to 3carbon atoms in the alkyl radical, β-methylsulphonamidoethyl orsulpho-n-butyl, R₅ and R₆ and the nitrogen atom to which they areattached are piperidine, morpholine, piperazine or pyrrolidine, Y ishydrogen, alkyl of 1 to 6 carbon atoms, hydroxy, --COOR₁₁ or --COONR₁₁R₁₂ and Z is --CN, --COOR₁₁ or --CONR₁₁ R₁₂, wherein R₁₁ and R₁₂ arehydrogen or alkyl of 1 to 3 carbon atoms.
 2. Light-sensitivephotographic material according to claim 1 wherein the layer whichcontains the dye is a resin backing layer on the reverse side to thephotosensitive layer.
 3. Light-sensitive material according to claim 2wherein the dye is of the formula ##STR16## wherein R₁ is alkyl of 1 to6 carbon atoms, R₂ is hydrogen or alkyl of 1 to 3 carbon atoms and R₅and R₆ are alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 2 to 4 carbonatoms or R₅ and R₆ together with the nitrogen atom to which they areattached are a piperidine, morpholine, piperazine or pyrrolidine ring.4. Light-sensitive photographic material according to claim 3 whereinthe dye corresponds to the formula ##STR17##
 5. Light-sensitivephotographic material according to claim 1 wherein the layer whichcontains the dye is an anti-halation underlayer.
 6. Light-sensitivephotographic material according to claim 5 wherein the dye correspondsto the formula ##STR18## wherein R₁ is alkyl of 1 to 6 carbon atoms, R₂is hydrogen or alkyl of 1 to 3 carbon atoms and R₅ and R₆ are alkyl of 1to 4 carbon atoms, hydroxyalkyl of 2 to 4 carbon atoms or R₅ and R₆together with the nitrogen atom to which they are attached are apiperidine, morpholine, piperazine or pyrrolidine ring. 7.Light-sensitive photographic material according to claim 6 wherein thedye corresponds to the formula ##STR19##
 8. Light-sensitive photographicmaterial according to claim 1 wherein the layer which contains the dyeis a colloid filter layer between light-sensitive layers. 9.Light-sensitive photographic material according to claim 8 wherein thedye is present as an oil dispersion.
 10. Light-sensitive photographicmaterial according to claim 8, wherein the dye corresponds to theformula ##STR20## wherein R₁ is alkyl of 1 to 6 carbon atoms, R₂ ishydrogen or alkyl of 1 to 3 carbon atoms and R₅ and R₆ are alkyl of 1 to4 carbon atoms, hydroxyalkyl of 2 to 4 carbon atoms or R₅ and R₆together with the nitrogen atom to which they are attached are apiperidine, morpholine, piperazine or pyrrolidine ring. 11.Light-sensitive photographic material according to claim 10 wherein thedye corresponds to the formula ##STR21##